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WO2012061706A1 - Navette double de chaînes polymeryl de polyoléfine - Google Patents

Navette double de chaînes polymeryl de polyoléfine Download PDF

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Publication number
WO2012061706A1
WO2012061706A1 PCT/US2011/059326 US2011059326W WO2012061706A1 WO 2012061706 A1 WO2012061706 A1 WO 2012061706A1 US 2011059326 W US2011059326 W US 2011059326W WO 2012061706 A1 WO2012061706 A1 WO 2012061706A1
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WO
WIPO (PCT)
Prior art keywords
metal
hydrocarbyl
polyolefin
olefin
cation
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PCT/US2011/059326
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English (en)
Inventor
Timothy T. Wenzel
Thomas P. Clark
David R. Wilson
Sara B. Klamo
Daniel J. Arriola
Curt N. Theriault
Robert D. Froese
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Dow Global Technologies Llc
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Publication of WO2012061706A1 publication Critical patent/WO2012061706A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the invention generally relates to a process for preparing a metal-functionalized polyolefin and a composition useful therein, and to the metal-functionalized polyolefin prepared thereby and new non-metallic polymers prepared therefrom.
  • Telechelic polymers comprise polymeryl chains that contain functional groups at their chain ends. Many types of telechelic polymers are known. Examples include polymers that contain a hydroxyl group at each polymeryl chain end. Telechelic polymers can be used, for example, as rocket fuel binders and as ingredients in coatings, sealants, and adhesives.
  • Telechelic polymers have been prepared by a number of methods.
  • U.S. Patent Number 5,247,023 mentions telechelic polymers prepared from certain metal-functionalized polyolefins, e.g., intermediate hydrocarbon-based polymers containing borane at polymeryl chain ends or in polymer backbones thereof.
  • Such telechelic polymers have a statistical (i.e., essentially random) distribution of terminal functional groups.
  • a chain shuttling agent can transfer polymer chains between two distinct catalysts with different olefin monomer selectivities in a single polymerization reactor.
  • the resulting catalyst system produces polyolefins, including olefin block copolymers with alternating semicrystalline and amorphous segments and a number of desirable material properties, (see Arriola DJ, et al., Catalytic Production of Olefin Block Copolymers via Chain Shuttling Polymerization, Science, 2006; 312: 714-719).
  • WO 2005/090427 A2 page 19 defines the term "[chain] shuttling agent" as referring to a compound or mixture of compounds employed in the composition of WO 2005/090427 A2 that is capable of causing polymeryl chain exchange between at least two active catalyst sites of the catalysts included in the composition under the conditions of the polymerization.
  • WO 2005/090427 A2 goes on to mention on page 20 that by selecting different combinations of catalysts having differing comonomer incorporation rates as well as differing reactivities, and by combining various shuttling agents or mixtures of agents with these catalyst combinations, polymer products having segments of different densities or comonomer concentrations, different block lengths, and different numbers of such segments or blocks in each copolymer can be prepared.
  • WO 2005/090427 A2 goes on to mention on page 22 that the mixtures of shuttling agents include the reaction product or mixture formed by combining a shuttling agent that is an organometal (hydrocarbyl metal) compound with less than a stoichiometric quantity (relative to the number of hydrocarbyl groups) of a secondary amine or a hydroxyl compound.
  • WO 2005/090427 A2 does not specifically mention combining two organometals comprising different metals.
  • Sita et al. in WO 2009/061499 and Sita et al., everydayrestroke Redux: Scalable Production of Precision Hydrocarbons from AIR 3 (R Et or iBu) by Dialkyl Zinc Mediated Ternary Living Coordinative Chain-Transfer Polymerization, Angew. Chem. Int. Ed. 2010; 49: 1768-1772, mention, among other things, a process for preparation of polyolefins via living coordinative chain transfer polymerization with a metallocene-type catalyst that employs diethyl zinc (DEZ), triethyl aluminum (TEA), or triisobutylaluminum (TIB A).
  • DEZ diethyl zinc
  • TAA triethyl aluminum
  • TIB A triisobutylaluminum
  • the inventors discovered and the present invention generally provides, among other things, a composition and polymerization process capable of polymerizing olefin monomer(s) with a non- metallocene-type olefin polymerization catalyst (NMOP catalyst) in presence of a polymeryl chain shuttling agent (PCSA) and a repository compound, referred to herein as a polymeryl chain repository agent (PCRA), to give a useful metal-containing polyolefin polymeryl chain.
  • NMOP catalyst non- metallocene-type olefin polymerization catalyst
  • PCSA polymeryl chain shuttling agent
  • PCA polymeryl chain repository agent
  • the PCSA and PCRA are matched based on their relative chain transfer constants C trl and in such a way so as to advantageously enable the process to: metallate in situ in a facile, reversible manner the polyolefin polymeryl chain so as to give the metal-containing polyolefin polymeryl chain; reduce the amount of PCSA required relative to NMOP catalyst to sub-stoichiometric quantities, as the PCRA functions, in part, to reversibly store excess amount (quantity not immediately used by NMOP catalyst) of the polyolefin polymeryl chain in situ; ultimately produce new polyolefins or telechelic polymers that have at least one improved property (e.g., enhanced melt flow rate (MFR), lower number average molecular weight (M n ), or both), as the PCRA also functions, in part, to reversibly functionalize the polyolefin polymeryl chain in situ in a form from which such polyolefins or telechelic polymers can be readily prepared
  • the present invention provides a polymerization process for preparing a metal-functionalized polyolefin, the process comprising contacting a first olefin monomer with a mixture comprising ingredients (a), (b), and (c), or a reaction product of any portion thereof:
  • (Ci-C 2 o)hydrocarbyl the PCSA
  • first NMOP catalyst a catalytically-effective amount of a first non- metallocene-type olefin polymerization catalyst
  • the contacting is performed under olefin polymerizing conditions (described later) in such a way so as to polymerize the first olefin monomer and thereby prepare a metal-functionalized polyolefin
  • the first metal (Ci-C 2 o)hydrocarbyl comprises a first metal cation and at least one (Ci-C 2 o)hydrocarbyl (maximum number of (Ci-C 20
  • the present invention provides the metal-functionalized polyolefin prepared in the first embodiment.
  • the present invention provides a composition comprising the mixture of the aforementioned ingredients (a), (b), and (c), or the reaction product of any portion thereof; wherein the first non-metallocene-type olefin polymerization catalyst is characterizable as being capable of catalytically polymerizing a first olefin monomer under olefin polymerizing conditions so as to produce a metal-functionalized polyolefin that upon reacting with a quenching reagent substantially releases the metal therefrom and prepares a polyolefin having an enhanced melt flow rate (i.e., melt flow index).
  • the invention process polymerizes olefin monomer(s), and thereby prepares the metal- functionalized polyolefin.
  • the invention composition is useful in the invention process.
  • the metal-functionalized polyolefin is especially useful for preparing known and, preferably, new polyolefins and telechelic poly olefins.
  • the invention process enables facile synthesis of the metal-functionalized polyolefin without substantially decreasing catalyst efficiency of first NMOP catalyst (i.e., decreasing it by less than 10%) or, when two different non-metallocene-type olefin polymerization catalysts are employed, without preventing polymeryl chain shuttling between them, or both.
  • the telechelic polyolefins prepared by the invention process are especially useful as, for example, as rocket fuel binders and as ingredients in coatings, sealants, and adhesives.
  • the polyolefins prepared by the invention process are especially useful as, for example, synthetic lubricants and, especially for the olefin block copolymers (OBCs), elastic films for hygiene applications (e.g., for diaper covers); flexible molded goods for appliances, tools, consumer goods (e.g., toothbrush handles), sporting goods, building and construction, automotive, and medical applications; flexible gaskets and profiles for appliance (e.g., refrigerator door gaskets and profiles), building and construction, and automotive applications; adhesives for packaging (e.g., for use in manufacturing corrugated cardboard boxes), hygiene applications, tapes, and labels; and foams for sporting goods (e.g., foam mats), packaging, consumer goods, and automotive applications.
  • OBCs olefin block copolymers
  • elastic films for hygiene applications e.g., for diaper covers
  • Figure (Fig.) la shows a generic polymeryl chain shuttling scheme of the present invention employing a single catalyst.
  • Fig. lb shows another generic polymeryl chain shuttling scheme of the present invention employing a single catalyst.
  • Fig. lc shows a generic polymeryl chain shuttling scheme of the present invention that summarizes Figs, la and lb.
  • Fig. 2a shows a version of Fig. lc comprising a generic Zn-based PCSA/B-based PCRA polymeryl chain shuttling scheme employing a single catalyst.
  • Fig. 2b shows a version of Fig. lc comprising a generic Zn-based PCSA/Al-based PCRA polymeryl chain shuttling scheme employing a single catalyst.
  • Fig. 3 shows a generic polymeryl chain shuttling scheme of the present invention employing two different catalysts.
  • Figs. 4a to 4g show different reactions for preparing various functionalized polymer from the boron-containing PCRA, all of the present invention.
  • Figs. 5a to 5c show different reactions for preparing various functionalized polymer from the aluminum-containing PCRA, all of the present invention.
  • Fig. 6 shows a continuous flow polymerization reactor system.
  • Fig. 7 is a graphical plot of results of MFR versus zinc cation mole fraction for non- invention processes (0% and 100% mole fraction of zinc cation) and processes of Examples 11a to l ie and 12a to 12f.
  • the invention relates to the process for preparing a metal-functionalized polyolefin and the composition useful therein, and to the metal-functionalized polyolefin prepared thereby and new non-metallic polymers prepared therefrom, all as summarized previously.
  • any lower limit of a range of numbers, or any preferred lower limit of the range may be combined herein with any upper limit of the range, or any preferred upper limit of the range, to define a preferred aspect or embodiment of the range.
  • each range of numbers includes all numbers, both rational and irrational numbers, subsumed within that range (e.g., the range from about 1 to about 5 includes, for example, 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
  • the term “about” in a phrase referring to a numerical value may be deleted from the phrase to give another aspect or embodiment of the instant invention.
  • Preferably "about” means from 90 percent to 100 percent of the numerical value, from 100 percent to 110 percent of the numerical value, or from 90 percent to 110 percent of the numerical value.
  • the open-ended terms “comprising,” “comprises,” and the like (which are synonymous with “including,” “having,” and “characterized by") may be replaced by the respective partially closed phrases “consisting essentially of,” “consists essentially of,” and the like or the respective closed phrases “consisting of,” “consists of,” and the like to give another aspect or embodiment of the instant invention.
  • the term “characterizable” is open-ended and means distinguishable or capable of being distinguished.
  • the term “plurality” means two or more, wherein each plurality is
  • such preferred embodiments can be readily determined by: (i) selecting any single member from the Markush group, thereby limiting scope of the Markush group to the selected single member thereof; or (ii) deleting any single member from the Markush group, thereby limiting the Markush group to any one of the remaining member(s) thereof.
  • the member that is selected or deleted is based on one of the Examples or other species of the present invention described herein.
  • catalyst efficiency means weight in grams of polymer produced divided by weight in grams of a catalytic metal of a metal-containing precatalyst (e.g., first non- metallocene precatalyst) employed.
  • a metal-containing precatalyst e.g., first non- metallocene precatalyst
  • the catalytic metal is described later.
  • catalytically effective amount means a less-than-stoichiometric quantity sufficient for increasing rate of the polymerization of olefin monomer (s).
  • chain repository effective amount means a quantity that is sufficient to store a majority, and preferably at least 90 mole percent (mol ), of the poly olefin polymeryl chain as the metal-functionalized polyolefin.
  • chain shuttling effective amount means a quantity that is sufficient to transfer the polyolefin polymeryl chain between the first NMOP catalyst and the first metal
  • chain transfer constant means a ratio of a chain transfer rate constant to a monomer propagation rate constant according to equation (a):
  • M n is number average molecular weight of a test polyolefin prepared by quenching the metal-functionalized polyolefin, which is prepared according to the process of the first embodiment;
  • B is l/M n(naUve) , wherein M n(native) is number average molecular weight of a native polyolefin, wherein B is determined or calculated as described below;
  • C trl is chain transfer constant for the first metal
  • the M n(native) by running a series of at least 3 olefin polymerization reactions under the same set of polymerization conditions and at various levels of the PCSA and with a fixed amount of, or preferably in absence of the PCRA so as to produce polyolefins therefrom, measuring M n thereof by GPC as described later, and plotting 1/M n versus the mole ratios of PCSA to olefin monomer, wherein the resulting y-intercept of that plot would be equal to B.
  • the same set of polymerization conditions comprises same reactor model and polymerization temperature or, preferably, same reactor model, polymerization temperature and catalyst efficiency (i.e., catalyst conversion).
  • the reactor model is Parr batch reactor model number 4532; polymerization temperature is 120 degrees Celsius (°C); and catalyst conversion is 100,000 grams polyolefin per gram of metal of the non-metallocene-type precatalyst.
  • Equation (a) is particularly valuable for determining chain transfer constants for polymerizations conducted in continuous-flow stirred polymerization reactors with a constant olefin monomer conversion rate (e.g., about 90% conversion) and constant feed concentrations of the first and second metal (Ci-C 2 o)hydrocarbyl and olefin monomer, where
  • [PCRA], [PCSA] , and [M] are concentrations thereof in their respective feeds in an inert hydrocarbon solvent such as, for example, a mixed alkanes solvent such as an isoparaffin fluid.
  • an inert hydrocarbon solvent such as, for example, a mixed alkanes solvent such as an isoparaffin fluid.
  • (Ci-C 2 o)hydrocarbyl (synonymous with the term “(Ci-C 2 o)hydrocarbyl group” when not used in a proper noun (e.g., "first metal (Ci-C 20 )hydrocarbyl”)) means a hydrocarbon radical of from 1 to 20 carbon atoms.
  • Each hydrocarbon radical independently is aromatic (i.e., (C 6 - C 20 )aryl, e.g., phenyl) or non-aromatic (i.e., (Ci-C 20 )aliphatic radical); saturated (i.e., (Ci-C 20 )alkyl or (C 3 -C 20 )cycloalkyl) or unsaturated (i.e., (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, or
  • (C 3 -C 20 )cycloalkenyl straight chain (i.e., normal-(Ci-C 20 )alkyl) or branched chain (i.e., secondary-, iso-, or tertiary-(C 3 -C 20 )alkyl); cyclic ((i.e., (C6-C 20 )aryl, (C 3 -C 20 )cycloalkenyl, or (C 3 - C 20 )cycloalkyl, including mono- and poly-cyclic, fused and non-fused polycyclic, including bicyclic; at least 3 carbon atoms) or acyclic (i.e., (Ci-C 20 )alkyl, (C 2 -C 20 )alkenyl, or (C 2 -C 20 )alkynyl); or a combination of two or more thereof (e.g., (C 3 -Cio)cycloalkyl-(Ci-Ci 0 )
  • Each hydrocarbon radical independently is the same as or different from another hydrocarbon radical and independently is unsubstituted or substituted by at least one halo.
  • halo means fluoro, chloro, bromo, or iodo.
  • enhanced melt flow rate is a discovery of the present invention and means an increase in number of grams of a melt of the polyolefin prepared by the invention process (invention process polyolefin) that moves through an orifice in a fixed period of time when under an applied force, compared to number of grams of a melt of a reference polyolefin that moves through the same orifice under same MFR measurement conditions and using the MFR
  • MFR measurement conditions used to demonstrate the enhanced MFR of the invention process polyolefin are not critical so long as they are the same for both the invention process and reference polyolefins.
  • Preferred MFR measurement conditions comprise temperature of the melts is 190 °C; applied force is 2160-gram force; orifice is a 0.0825-inch (2.0955-millimeter) diameter orifice; and time period is 10 minutes.
  • the increase in MFR (enhanced MFR) observed for the invention process polyolefin demonstrates that the number average molecular weight (M n ) of the invention process polyolefin is lower than the M n of the reference polyolefin, and this indicates a synergistic interaction occurs between the first and second metal (Ci-C 2 o)hydrocarbyls, or reaction products thereof, in the invention process.
  • the enhanced MFR is measured for invention process polyolefins prepared from polymerizations conducted in continuous-flow stirred polymerization reactors with a constant olefin monomer conversion rate (e.g., about 90% conversion) and constant feed rates of the first and second metal (Ci-C 2 o)hydrocarbyl and olefin monomer.
  • the feed rates can be expressed as micromoles per minute.
  • MFR of the invention process polyolefin can, if desired, be visually observed by graphically plotting MFR on y-axis versus second metal cation mole fraction of 0.0%, 25%, 50%, and 100% (0.0, 0.25, 0.50, and 1.0 mole fraction, respectively) on x-axis.
  • the present synergistic interaction shows the increase of MFR of the invention process polyolefin as a point or line that plots above such a flat horizontal line at mole fraction of the second metal cation > 0.0% and ⁇ 100%.
  • the difference between the point and line or two lines at any particular value of mole fraction of the second metal cation > 0.0% and ⁇ 100% equals the increase in or enhancement of MFR and demonstrates the aforementioned synergistic interaction in the invention process.
  • the invention process preferably is characterizable as being capable of producing the invention process polyolefin having the enhanced MFR.
  • Group 1 , 2, 12, or 13 metal cation means a positive ionic form of an element of any one of Groups 1, 2, 12, and 13 of the Periodic Table of the Elements.
  • metal-functionalized polyolefin means a molecule or molecules comprising a polyolefin polymeryl chain bonded to a cation of an electropositive element (e.g., metal cation), preferably of Groups 1 , 2, 12, or 13.
  • an electropositive element e.g., metal cation
  • metal (Ci-C 2 o)hydrocarbyl means a molecule or molecules comprising at least one (Ci-C 2 o)hydrocarbyl bonded to a cation of an electropositive element.
  • non-metallocene-type precatalyst means a substance or molecule comprising the catalytic metal and at least one ligand bonded thereto, wherein each of the at least one ligand lacks an unsubstituted or substituted cyclopentadiene or anionic derivative thereof, wherein the substance or molecule is capable of increasing rate of a reaction of olefin monomer(s) to give the polyolefin polymeryl chain without the substance or molecule being changed.
  • Substituted cyclopentadiene includes benzo-fused cyclopentadiene.
  • the catalytic metal has a positive formal oxidation state, i.e., formally is a cation. Examples of the catalytic metal are metals of Groups 3 to 9, preferably Groups 3 to 6, and more preferably Group 4, of the Periodic Table of the Elements.
  • a preferred Group 4 metal is hafnium, zirconium, or titanium.
  • non-metallocene-type olefin polymerization catalyst means a substance of molecule comprising, or a reaction product of, a mixture comprising the non-metallocene-type precatalyst and at least one activating co-catalyst.
  • the NMOP catalyst lacks the unsubstituted or substituted cyclopentadiene or anionic derivative thereof.
  • olefin monomer means a molecule or molecules that can directly produce a repeat unit of a polyolefin wherein each molecule independently contains a non-aromatic carbon- carbon triple bond or, preferably, a non-aromatic carbon-carbon double bond and can be polymerized to ultimately form a polyolefin.
  • organic solvent polymerizing conditions means a set of reaction parameters such as, for example, temperature, pressure, time, rate of heating or cooling, type of reactor employed, and presence or absence of additional ingredients (e.g., solvent, molecular weight control agent, or a combination thereof). These conditions are described later.
  • polyolefin polymeryl chain means a radical or polyradical (i.e., at least two radicals) of a polymer comprising repeat units comprising residuals of olefin monomer(s).
  • portion referring to the mixture of ingredients means a structural part (e.g., metal cation part of metal (Ci-C 2 o)hydrocarbyl) or whole of one of the ingredients, or a combination of any two or more structural parts or wholes of any two or more ingredients.
  • reaction product means a new substance resulting from a reversible or, preferably, irreversible chemical reaction between two or more reactant substances.
  • Fig. la shows an invention generic polymeryl chain shuttling scheme of the present invention employing a single catalyst, catalyst 1 .
  • the polymeryl chain (“Polymeryl") reversibly shuttles from catalyst 1 to a PCSA (Exchange 1), and from the PCSA to the PCRA (Exchange 2).
  • Fig. lb shows another invention generic polymeryl chain shuttling scheme of the present invention employing a single catalyst.
  • Figs. 2a and 2b show different versions of Fig. lc comprising an invention embodiment of the shuttling scheme of Fig. lc.
  • Fig. 2a shows a generic Zn-based PCS A/B -based PCRA polymeryl chain shuttling scheme employs a single catalyst 1 .
  • Fig. 2b shows a generic Zn-based PCSA/Al-based PCRA polymeryl chain shuttling scheme employing a single catalyst 1 .
  • Fig. 3 shows an invention polymeryl chain shuttling scheme employing two different catalysts, catalyst 1 and catalyst 2 .
  • the polymeryl chain reversibly shuttles between catalyst 1 and PCSA, and between the PCSA and either catalyst 2 or the PCRA.
  • the first NMOP catalyst is capable of polymerizing the first olefin monomer (or the first olefin monomer and at least one olefin comonomer, as the case may be) so as to produce a growing polyolefin polymeryl chain. Chain growth occurs when the polyolefin polymeryl chain is bonded to the catalytic metal of the first NMOP catalyst or catalytic metal of another catalyst, if any, as described later herein.
  • the first metal (Ci-C 2 o)hydrocarbyl is capable of functioning as, or forming in situ, the polymeryl chain repository agent (PCRA) and the second metal (Ci-C 2 o)hydrocarbyl is capable of functioning as, or forming in situ, the polymeryl chain shuttling agent (PCSA).
  • the PCSA, PCRA, olefin monomer, and the first NMOP catalyst can unpredictably act together so as to synergistically increase (enhance) MFR and concomitantly lower M n of the polyolefin polymeryl chain as demonstrated as described previously.
  • the amount of the polyolefin polymeryl chain that is reversibly stored and functionalized as the metal- functionalized polyolefin by the PCRA is at least an amount of the polyolefin polymeryl chain that is in excess of the combined bonding capacities of the second metal cation and catalyst metal of the first NMOP catalyst, and preferably is a majority of the polyolefin polymeryl chain.
  • the invention process prepares the metal-functionalized polyolefin via a nonliving polymerization reaction.
  • Non-living polymerization reaction is distinguishable from a living polymerization reaction by polydispersity index (PDI).
  • PDI polydispersity index
  • living polymerization means a reaction producing a polyolefin having a PDI of at most 1.80 and, in some cases, at most 1.40.
  • the contacting step of the invention process does not employ, and the mixture does not contain, a metallocene-type catalyst (i.e., as an additional catalyst in the contacting step).
  • the mixture in the contacting step of the invention process is prepared with, and the invention process employs, only one non-metallocene-type precatalyst (i.e., and only the first NMOP catalyst).
  • the mixture is prepared with, and the invention process employs, only two non-metallocene-type precatalysts (i.e., prepared from the first non- metallocene-type precatalyst and a different second non-metallocene-type precatalyst) such that there are only the first and second NMOP catalysts.
  • the PCSA would also shuttle the polyolefin polymeryl chain between the first and second NMOP catalysts
  • the invention process contemplates employing a batch or, preferably, continuous-flow polymerization method and reactor for the contacting step.
  • the invention olefin polymerization reactions can be run in one reactor or multiple (two or more) reactors with one NMOP catalyst and optionally one or more other catalysts.
  • at least two catalysts are introduced into a single reactor and placed under the olefin polymerization conditions, wherein at least the first one of the catalysts is the first NMOP catalyst and each catalyst inherently produces a mixture or blend of different polyolefins or polyolefin copolymers.
  • the term "copolymer” means a molecule comprising repeat units comprising residuals of at least two, preferably only two, different monomers.
  • a relatively high molecular weight polyolefin (M w from 100,000 g/mol to over 1 ,000,000 g/mol, more preferably 200,000 g/mol to 500,000 g/mol) is formed from one of the catalysts while a polyolefin of a relatively low molecular weight (M w 2,000 g/mol to 300,000 g/mol) is formed from another of the catalysts.
  • the at least two catalysts can have similar or different comonomer incorporation abilities, different polymer molecular weight producing capabilities, or a combination thereof.
  • the resulting mixture or blend of different polyolefin copolymers will have properties dependent, in part, on the ratio of the at least two catalysts that are employed in the single reactor. Suitable combinations of polyolefin molecular weight, comonomer incorporation ability, processes, and ratios of catalysts for such products are disclosed in U.S. Pat. No. 6,924,342.
  • Examples of suitable processes and systems employing multiple reactors include such processes and systems as are disclosed in U.S. Pat. No. 3,914,342.
  • the multiple reactors preferably two reactors, can be operated in series or in parallel, with at least the first NMOP catalyst being employed in at least one of the reactors.
  • Polyolefin products from these reactors can have similar or different densities.
  • the final polyolefin polymer product is a mixture or blend of effluents of different polyolefins from the at least two reactors.
  • the effluents of different polyolefins are preferably combined by mixing or blending prior to being subjected to de volatilization so as to more easily result in a uniform mixing or blending of the different polyolefins.
  • the molecular weight of the different polyolefins from the at least two reactors is nearly the same but the densities vary to the extent that one of the reactors produces a first polyolefin polymer with density in the range of 0.865-0.895, while another reactor produces a second polyolefin polymer with a different density in the range of 0.885-0.950.
  • two reactors and two catalysts, at least one of which is the first NMOP catalyst are employed, such a dual reactor/dual catalyst process allows for the preparation of a mixture or blend of polyolefin polymers with tailored properties.
  • two reactors are connected in series, that is, the effluent from a first reactor is charged to a second reactor and, optionally, fresh monomer, solvent and hydrogen are added to the second reactor.
  • the first NMOP catalyst can be employed in the first or second reactor or both.
  • Olefin polymerization conditions are adjusted in the second reactor so that they are different from the olefin polymerization conditions that are employed in the first reactor such that a weight ratio of weight of the polyolefin polymer produced in the first reactor to weight of the polyolefin polymer produced in the second reactor is ideally in the range of from 20:80 to 80:20.
  • This embodiment of a dual reactor process is capable of producing a mixture or blend of different polyolefin polymers having broadened molecular weight distribution or polydispersity index (PDI).
  • the invention process produces a mixture or blend of different polyolefin polymers that comprises high and low molecular weight polyolefin polymer components.
  • one of the two reactors of the dual reactor embodiment contains a heterogeneous Ziegler-Natta catalyst or a chromium containing catalyst, such as one of the numerous such catalysts known in the art.
  • Ziegler-Natta catalysts include, but are not limited to, titanium-based catalysts supported on MgCl 2 , and additionally comprise compounds of aluminum containing at least one aluminum-alkyl bond.
  • Suitable Ziegler-Natta catalysts and their preparation include, but are not limited to, those disclosed in U.S. Pat. Nos. 4,612,300, 4,330,646, and 5,869,575.
  • Suitable chromium based catalysts are those disclosed in U.S. Pat. Nos. 4,981,927, 4,835,219, 4,564,660, 4,173,548, 3,953,413, and elsewhere.
  • the first NMOP catalyst is contained in the same or different one of the two reactors as the aforementioned catalysts.
  • the invention process employs olefin polymerizing conditions. Olefin polymerizing conditions independently refer to reaction conditions such as solvent(s), atmosphere(s),
  • the invention process is independently run under an inert atmosphere (e.g., under an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof).
  • an inert atmosphere e.g., under an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof.
  • Other atmospheres are contemplated, however, and these include sacrificial olefin in the form of a gas and hydrogen gas (e.g., as a polymerization termination agent or molecular weight control agent).
  • the invention process independently is run without any solvent, i.e., is a neat process that is run in a neat mixture of ingredients (e.g., ingredients (a) to (c)).
  • the neat mixture further contains additional ingredients (e.g., catalyst stabilizer such as triphenylphosphine) other than solvent(s).
  • the invention process is run with a solvent or mixture of two or more solvents, i.e., is a solvent-based process that is run as a solvent- containing mixture of ingredients, and at least one solvent, e.g., an aprotic solvent.
  • the neat process or solvent-based process is run at a temperature of the neat mixture or solvent- containing mixture of from -20 °C to about 300 °C. In some embodiments, the temperature is at least 30 °C, and more preferably at least 40 °C. In some embodiments, the temperature is at least 100 °C.
  • the temperature is 200 °C or lower.
  • a convenient temperature is from about 130 °C to about 190 °C (e.g., 150 °C or 170 °C or 190 °C).
  • the invention process independently is run under a pressure of from about 0.9 atmospheres (atm) to about 10 atm (from about 91 kiloPascals (kPa) to about 1010 kPa). More preferably, the pressure is about 101 kPa).
  • olefin monomers useful in the invention process are those that are polymerizable under the conditions thereof.
  • olefin monomers (including olefin comonomers when there are at least two olefin monomers) useful in the invention process are olefinic (C 2 -
  • C 40 hydrocarbons consisting of carbon and hydrogen atoms and containing at least 1 , and preferably no more than 3, and more preferably no more than 2, carbon-carbon double bonds.
  • from 1 to 4 hydrogen atoms of the (C 2 -C 4 o)hydrocarbons are replaced, each by a halogen atom, preferably fluoro or chloro to give halogen atom-substituted olefinic (C 2 - C 40 )hydrocarbons as the useful olefin monomers.
  • the olefinic (C 2 -C 40 )hydrocarbons (not halogen atom-substituted) are preferred.
  • Still more preferred olefin monomers are ethylene and
  • (C 3 -C 0 )olefins examples are alpha-olefins, cyclic olefins, styrene, and cyclic or acyclic dienes.
  • the invention process employs the first olefin monomer and at least one other olefin monomer (i.e., at least one olefin comonomer), wherein the at least one other olefin monomer is the alpha-olefin, and more preferably a (C 3 -C 40 )alpha-olefin.
  • the (C 3 -C 40 )alpha-olefin is a (C 4 -C 40 )alpha-olefin, more preferably a (C 6 -C 40 )alpha- olefin, still more preferably a (C 7 -C 40 )alpha-olefin, and even more preferably a (C 8 -C 40 )alpha-olefin.
  • the cyclic olefin is a (C 3 -C 0 )cyclic olefin.
  • the cyclic or acyclic diene is a (C -C 0 )diene, preferably an acyclic diene, more preferably an acyclic conjugated (C -C 0 )diene, more preferably an acyclic 1,3-conjugated (C -C 0 )diene, and still more preferably 1,3-butadiene.
  • Polyolefins that can be made by an invention process include, for example, polyethylene and copolymers (interpolymers) that comprise residuals of ethylene and at least one (C 3 -C 40 )olefin.
  • Preferred homopolymers are polyethylene and polypropylene.
  • Preferred copolymers are those prepared by co-polymerizing a mixture of at least two olefin monomers (i.e., a mixture of the first olefin monomer and at least one olefin comonomer) such as, for example, ethylene/propylene, ethylene/ 1-butene, ethylene/1 -pentene, ethylene/ 1-hexene, ethylene/4-methyl- 1-pentene, ethylene/1- octene, ethylene/styrene, ethylene/propylene/butadiene and other EPDM terpolymers.
  • olefin monomers i.e., a mixture of the first olefin monomer and at least one olefin comonomer
  • the polyolefin is an ethylene homopolymer (e.g., a high density polyethylene), an ethylene/alpha- olefin copolymer (i.e., poly(ethylene alpha-olefin) copolymer such as, for example, a poly(ethylene 1-octene)), or an ethylene/alpha-olefin/diene interpolymer (i.e., a poly(ethylene alpha-olefin diene) terpolymer such as, for example, a poly(ethylene 1-octene 1,3-butadiene).
  • ethylene homopolymer e.g., a high density polyethylene
  • an ethylene/alpha- olefin copolymer i.e., poly(ethylene alpha-olefin) copolymer such as, for example, a poly(ethylene 1-octene)
  • an ethylene/alpha-olefin/diene interpolymer i.e.,
  • (Ci-C 20 )hydrocarbyl is (Ci-C 20 )alkyl, (C 3 -C 20 )cycloalkyl, (C6-Ci 8 )aryl, or a composite radical of at least two thereof.
  • An example of the composite radical is
  • (C6)aryl-(Ci-Ci 2 )alkyl (C6)aryl-(Ci-Ci 2 )alkyl.
  • (Ci-C 20 )alkyl means a straight or branched saturated hydrocarbon radical of from 1 to 20 carbon atoms (e.g., methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, 1,1- dimethylethyl, etc.). Any hydrocarbon radical can be unsubstituted or substituted with phenyl, naphthyl, or halo.
  • (C6-Ci 8 )aryl means a mono-, bi- or tricyclic aromatic hydrocarbon radical of from 6 to 18 carbon atoms, of which at least from 6 to 14 of the carbon atoms are aromatic ring carbon atoms, and the mono-, bi- or tricyclic radical comprises 1, 2 or 3 rings, respectively; wherein the 1 ring is aromatic and the 2 or 3 rings independently are fused or non-fused and at least one of the 2 or 3 rings is aromatic.
  • (C 3 -C 20 )cycloalkyl means a saturated or unsaturated (but not aromatic) cyclic hydrocarbon radical of from 3 to 20 carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.)
  • polymeryl chain shuttling agent or PCSA means the second metal
  • the PCSA is a molecule characterizable, without limitation, as functioning in the invention process in such a way that polymer chains are transferred between the PCRA and the first NMOP catalyst in a single polymerization reactor.
  • the PCSA further transfers the polyolefin polymeryl chains in a single polymerization reactor between the two (or more) distinct NMOP catalysts.
  • PCSAs comprise a metal that is Al, B, or Ga, the second metal cation being in a formal oxidation state of +3; or, preferably, a second metal cation that is Zn or Mg in a formal oxidation state of +2.
  • Preferred chain shuttling agents are described in U.S. Patent Application Publication Number US
  • PCSAs suitable for use in the invention process include diethylzinc, di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminum
  • PCRA polymeryl chain repository agent
  • the PCRA is independently selected from the aforementioned list of PCSAs in accordance with the chain transfer constants C trl and C ⁇ , respectively, wherein > C trl and C trl > 0.
  • the second metal (Ci-C 2 o)hydrocarbyl (PCSA) is a zinc (Ci-C 2 o)hydrocarbyl and the first metal (Ci-C 20 )hydrocarbyl (PCRA) is a boron (Ci-C 20 )hydrocarbyl or, more preferably, an aluminum (Ci-C 20 )hydrocarbyl.
  • the PCSA is diethylzinc, di(i-butyl)zinc, di(n- hexyl)zinc, ethylzinc (2,6-diphenylphenoxide), or ethylzinc (t-butoxide); and the PCRA is triethylaluminum, trioctylaluminum, i-butylaluminum bis(dimethyl(t-butyl)siloxane), i- butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), bis(n- octadecyl)i-butylaluminum, i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t- butylphenoxide, n-octylaluminum di(eth)
  • the contact step is carried out at low rates of propagation of polyolefin polymeryl chains and sufficiently long reactor residence time (e.g., in a continuous-flow reactor), such that a majority of polyolefin polymeryl chain ends are functionalized with a boron species, as determined by nuclear magnetic resonance (NMR) spectroscopy.
  • NMR nuclear magnetic resonance
  • the rates of propagation can be higher and reactor residence times can be shorter than those for the boron (Ci-C 20 )hydrocarbyl.
  • the first metal (Ci-C 20 ))hydrocarbyl, or any reaction product thereof, (PCRA) does not substantially decrease (any decrease is less than 10%) catalyst efficiency of the first non-metallocene-type olefin polymerization catalyst in the contacting step compared to a reference catalyst efficiency of the first non-metallocene-type olefin polymerization catalyst when the first metal (Ci-C 20 ))hydrocarbyl is absent.
  • the contacting step comprises a continuous-flow polymerization process step operating in a continuous-flow reactor (preferably a continuous-flow stirred reactor) and the process further comprises a preliminary step of feeding the first olefin monomer, polymeryl chain repository effective amount of the first metal (Ci-C 20 ))hydrocarbyl (PCRA), polymeryl chain shuttling effective amount of the second metal (Ci-C 20 ))hydrocarbyl (PCSA), and first non- metallocene-type olefin polymerization catalyst into the continuous-flow reactor and a subsequent step of removing the metal-functionalized polyolefin from the continuous-flow reactor so as to provide a removed metal-functionalized polyolefin.
  • a continuous-flow reactor preferably a continuous-flow stirred reactor
  • the polymeryl chain shuttling effective amount of the second metal (Ci-C 20 ))hydrocarbyl (PCSA) is less on a mole basis than the polymeryl chain repository effective amount of the first metal (Ci-C 20 ))hydrocarbyl (PCRA) and less on a mole basis than the catalytically effective amount of the first non-metallocene-type precatalyst and any other precatalyst.
  • a sum of the polymeryl chain repository effective amount plus the polymeryl chain shuttling effective amount is, on a mole basis, greater than the catalytically effective amount of the first non-metallocene-type precatalyst (and preferably any catalytically effective amount of any other precatalyst (e.g., second non-metallocene-type precatalyst)).
  • Preferred metal (Ci-C 2 o)hydrocarbyl for the PCS A and PCRA are aluminum
  • (Ci-C 20 )hydrocarbyl or zinc (Ci-C 20 )hydrocarbyl. More preferred are aluminum (Ci-C 20 )alkyl, boron (Ci-C 20 )alkyl, gallium (Ci-C 20 )alkyl, magnesium (Ci-C 20 )alkyl, or zinc (Ci-C 20 )alkyl.
  • the first metal (Ci-C 20 ))hydrocarbyl (PCRA) is a boron (Ci-C 20 ))hydrocarbyl.
  • the second metal (Ci-C 20 ))hydrocarbyl (PCSA) is aluminum
  • the second metal (Ci-C 20 ))hydrocarbyl is gallium (Ci-C 20 ))hydrocarbyl.
  • the second metal (Ci-C 20 ))hydrocarbyl is magnesium (Ci-C 20 ))hydrocarbyl.
  • each such (Ci-C 20 ))hydrocarbyl independently is a (Ci-C 20 )alkyl, and in some embodiments (Ci-Cio)alkyl or (Ci-C 5 )alkyl.
  • the first metal (Ci-C 20 ))hydrocarbyl (PCRA) is an aluminum
  • the second metal (Ci-C 20 ))hydrocarbyl (PCSA) is gallium (Ci-C 20 ))hydrocarbyl.
  • the second metal (Ci-C 20 ))hydrocarbyl is magnesium (Ci-C 20 ))hydrocarbyl.
  • the second metal (Q- C 2 o))hydrocarbyl is zinc (Ci-C 20 ))hydrocarbyl.
  • the second metal (d- C 20 ))hydrocarbyl is a mixture of any two of the foregoing gallium, magnesium, and zinc (d-
  • each such (Ci-C 20 ))hydrocarbyl independently is a (Ci-C 20 )alkyl, and in some embodiments (Ci-Cio)alkyl or (Ci-C5)alky.
  • the second metal (Ci-C 20 ))hydrocarbyl (PCSA) is a zinc
  • the first metal (Ci-C 20 ))hydrocarbyl is boron (Ci-C 20 ))hydrocarbyl.
  • the first metal (Ci-C 20 ))hydrocarbyl is aluminum (Ci-C 20 ))hydrocarbyl.
  • the first metal (Ci-C 20 ))hydrocarbyl is gallium (Ci-C 20 ))hydrocarbyl.
  • the first metal (Ci-C 20 ))hydrocarbyl is magnesium (Ci-C 20 ))hydrocarbyl.
  • the first metal (Q- C 20 ))hydrocarbyl is a mixture of any two of the foregoing boron, aluminum, gallium, and magnesium (Ci-C 2 o))hydrocarbyls.
  • each such (Ci-C 2 o))hydrocarbyl independently is a (Ci-C 2 o)alkyl, and in some embodiments (Ci-Cio)alkyl or (Ci-C 5 )alky.
  • the first metal cation of or from the first metal (Ci-C 2 o))hydrocarbyl (PCRA) is a Group 13 metal cation and the second metal cation of or from the second metal (Q- C 20 ))hydrocarbyl (PCSA) is a zinc cation.
  • the first metal (Ci-C 20 ))hydrocarbyl is an aluminum (Ci-C 20 ))alkyl, which comprises an aluminum cation and from 1 to 3 (Ci-C 20 ))alkyl; or a boron (Ci-C 20 ))alkyl, which comprises a boron cation and from 1 to 3 (Ci-C 20 ))alkyl; and the second metal (Ci-C 20 ))hydrocarbyl is a zinc (Cl-C20)alkyl, which comprises a zinc cation and 1 or 2 (Ci-C 20 ))alkyl.
  • the first metal (Ci-C 20 ))hydrocarbyl is the aluminum (d- C 20 ))alkyl, which is an aluminum (Ci-C6))alkyl; and the zinc (Ci-C 20 ))alkyl is a zinc (Ci-C6))alkyl.
  • the aluminum (Ci-C 20 )hydrocarbyl (e.g., ((Ci-C 20 )alkyl 3 Al) can be obtained from commercial sources or are readily prepared by contacting an aluminum halide (e.g., A1C1 3 ) with 3 mole equivalents of a (Ci-C 20 )hydrocarbyl Grignard reagent or, preferably, a (Ci-C 20 )hydrocarbyl lithium.
  • the boron (Ci-C 20 )hydrocarbyl e.g., ((Ci-C 20 )alkyl 3 B) can be obtained from commercial sources or are readily prepared by contacting triethylborate (B(OCH 2 CH 3 ) 3 ) with the aluminum (Ci-C 20 )hydrocarbyl. If desired, the product boron (Ci-C 20 )hydrocarbyl can be evaporated in vacuo from aluminum ethoxide byproduct and collected so as to give an isolated and purified boron (Ci-C 20 )hydrocarbyl.
  • triethylborate B(OCH 2 CH 3 ) 3
  • the product boron (Ci-C 20 )hydrocarbyl can be evaporated in vacuo from aluminum ethoxide byproduct and collected so as to give an isolated and purified boron (Ci-C 20 )hydrocarbyl.
  • the gallium (Ci-C 20 )hydrocarbyl (e.g., ((Ci-C 20 )alkyl 3 Ga) can be obtained from commercial sources or are readily prepared by contacting a gallium halide (e.g., GaCl 3 ) with 3 mole equivalents of a (Ci-C 20 )hydrocarbyl Grignard reagent or, preferably, a (Ci-C 20 )hydrocarbyl lithium.
  • the magnesium (Ci-C 20 )hydrocarbyl e.g., ((Ci-C 20 )alkyl 2 Mg) can be obtained from commercial sources or are readily prepared by contacting magnesium metal with 3 mole equivalents of a (Ci-C 20 )hydrocarbyl-bromide or (Ci-C 20 )hydrocarbyl-iodide.
  • the zinc (Ci-C 20 )hydrocarbyl e.g., ((Ci-C 20 )alkyl 2 Zn
  • the zinc (Ci-C 20 )hydrocarbyl can be obtained from commercial sources or are readily prepared by contacting a zinc -copper couple with 3 mole equivalents of a (Ci-C 20 )hydrocarbyl-bromide or (Ci-C 20 )hydrocarbyl-iodide.
  • the contacting can be performed in an aprotic solvent such as, for example, tetrahydrofuran or toluene under an inert gas atmosphere such as, for example, an atmosphere of nitrogen gas, helium, or argon gas, at a temperature of from about -80 °C to about 50 °C.
  • an aprotic solvent such as, for example, tetrahydrofuran or toluene
  • an inert gas atmosphere such as, for example, an atmosphere of nitrogen gas, helium, or argon gas
  • the process further comprises, in a preliminary step, mixing together the first non-metallocene-type precatalyst and at least one first co-catalyst in such a way so as to prepare the first NMOP catalyst before employing the first NMOP catalyst in the contacting step.
  • the contacting step further employs at least one second olefin monomer (i.e., olefin comonomer(s)) and copolymerizes the first and second olefin monomers, and thereby prepares the metal-functionalized polyolefin as a metal-functionalized olefin copolymer.
  • at least one second olefin monomer i.e., olefin comonomer(s)
  • the contacting step further employs the at least one second olefin monomer and the mixture in the contacting step further contains an ingredient (d): a catalytically effective amount of a second non-metallocene-type olefin polymerization (NMOP) catalyst, wherein the second non- metallocene-type olefin polymerization catalyst comprises a second non-metallocene-type precatalyst and at least one second co-catalyst, or a reaction product thereof; wherein the first and second co-catalysts are the same as or different than each other; the first and second non- metallocene-type precatalysts are different from each other; and the first and second NMOP catalysts are different from each other and are both catalytically active in the contacting step; and wherein the contacting step copolymerizes the first and second olefin monomers, and thereby prepares the metal-functionalized polyolefin as a
  • the second NMOP catalyst has a different monomer selectivity than that of the first NMOP catalyst.
  • the process further employs at least three, preferably at most four, different olefin monomers, which includes the first olefin monomer.
  • the olefin copolymer is an olefin block copolymer.
  • the metal-functionalized polyolefin contains at least one type of metal cation. As mentioned previously, a majority of the metal cation of the metal-functionalized polyolefin is the third metal cation. Preferably, at least 70 mol , more preferably at least 80 mol , and still more preferably at least 90 mol of the metal cation of the metal-functionalized polyolefin is the third metal cation. As mentioned previously, the third metal cation is the same element as the first metal cation of the first metal (Ci-C 2 o)hydrocarbyl (PCRA). The third metal cation can be exchanged for a fourth metal cation if desired.
  • the metal-functionalized polyolefin contains one metal cation per molecule and is useful for preparing the polyolefin. In other embodiments the metal-functionalized polyolefin contains two metal cations per molecule and is useful for preparing the polyolefin or telechelic polyolefin. In a branched polyolefin polymeryl chain, the metal-functionalized polyolefin contains at least three metal cations per molecule and is useful for preparing the polyolefin or functionalized polyolefins containing at least three functional groups per molecule.
  • the metal-functionalized polyolefin can further comprise additional ligands so as to satisfy the coordinating capacity of the third metal cation.
  • additional ligands are the (Ci-C 2 o)hydrocarbyl,
  • the (Ci-C 2 o)alkoxide and hydroxide can originate from, for example, quenching the mixture in the contacting step with a (Ci-C 2 o)alcohol or water after polymerization.
  • the invention process further comprises contacting the metal-functionalized polyolefin (preferably the removed metal-functionalized polyolefin) with a quenching or functionalization reagent in such a way so as to substantially release the metal therefrom and thereby respectively prepare the polyolefin or non-metallic functional group-containing polyolefin (e.g., telechelic polyolefin).
  • the quenching reagent is a protic solvent such as 2-propanol.
  • the polyolefin is characterizable by an enhanced melt flow rate (i.e., melt flow index); a polydispersity index of 1.90 or greater; or a combination thereof.
  • melt flow rate (MFR) of the polyolefin produced from the metal- functionalized polyolefin prepared by the invention process is enhanced, i.e., increased. Since it is known that MFR and number average molecular weight (M n ) are inversely correlated, the M n of the invention polyolefin is lower.
  • the enhanced MFR and decreased M n are compared to reference MFR and M n of a reference polyolefin prepared by a non-invention process employing the first metal (Ci-C 20 )hydrocarbyl (PCRA) or second metal(Ci-C 20 )hydrocarbyl (PCSA), but not both.
  • the invention process produces the invention polyolefin wherein the MFR thereof is at least 20%, more preferably at least 50%, still more preferably at least 90%, and even more preferably at least 100% greater than the reference MFR of the reference polyolefin.
  • the enhanced MFR is greater than 1.20 grams per 10 minutes (g/10 min.), more preferably greater than 1.60 g/10 min., and still more preferably greater than 2.0 g/10 min., whereas the reference MFR is 1.1 g/10 mi. or less.
  • the polyolefin produced by the invention process has a polydispersity index (PDI) of at least 1.90, more preferably at least 2.0, in some embodiments at least 2.40, in some embodiments at least 3.0, in some embodiments at least 4.0, and in some embodiments at least 5.0.
  • PDI polydispersity index
  • the PDI is at most 7.5, in some embodiments at most 6.0, in some embodiments at most 5.0, in some embodiments at most 4.0, and in some embodiments at most 3.0.
  • the PDI is from 2.0 to 3.0 and in other embodiments from 2.0 to 2.2.
  • the process further comprises contacting the metal-functionalized polyolefin (preferably the removed metal-functionalized polyolefin) with the functionalization reagent in such a way so as to prepare a non-metallic functional group-containing polyolefin (i.e., a polyolefin containing at least one functional group, wherein the at least one functional group does not contain a metal).
  • a non-metallic functional group-containing polyolefin i.e., a polyolefin containing at least one functional group, wherein the at least one functional group does not contain a metal.
  • This polyolefin contains non-metallic functional groups in place of the metallic functional groups of the metal-functionalized polyolefin.
  • the non-metallic functional group-containing polyolefin is a telechelic polyolefin that contains at least two non- metallic functional groups that each contains at least one oxygen, nitrogen, or halogen atom.
  • the functionalization reagent is useful for synthesizing such non-metallic functional groups.
  • the third metal cation is boron cation
  • Fig. 4a shows an invention reaction for preparing at least one product comprising a polymer
  • polymeryl-H wherein the at least one product is prepared from the B-based PCRA-polymeryl chain complex by contacting the latter with molecular hydrogen in presence of a hydrogenolysis catalyst (e.g., Pd/C).
  • a hydrogenolysis catalyst e.g., Pd/C
  • a displacement catalyst e.g., Ni(0 2 CCH 3 ) 2
  • Fig. 4c shows an invention reaction for preparing at least one product comprising a mono- or bis-hydroxyl-terminated polymer (i.e., polymeryl-OH or HO-polymerylene-OH), wherein the at least one product is prepared from the B -based PCRA-polymeryl chain complex by contacting the latter with an oxidant such as hydrogen peroxide in presence of sodium hydroxide.
  • a mono- or bis-hydroxyl-terminated polymer i.e., polymeryl-OH or HO-polymerylene-OH
  • Fig. 4d shows an invention reaction for preparing at least one product comprising a mono- or bis-amino-terminated polymer (i.e., polymeryl-NH 2 or H 2 N-polymerylene-NH 2 ), wherein the at least one product is prepared from the B -based PCRA-polymeryl chain complex by contacting the latter with a source of ammonia and a mild oxidant such as sodium hypochlorite.
  • a mono- or bis-amino-terminated polymer i.e., polymeryl-NH 2 or H 2 N-polymerylene-NH 2
  • Fig. 4e shows an invention reaction for preparing at least one product comprising a mono- or bis-RS-terminated polymer (i.e., polymeryl-SR or RS-polymerylene-SR, wherein R is
  • Fig. 4f shows an invention reaction for preparing at least one product comprising a mono- or bis-bromo-terminated polymer (i.e., polymeryl-Br or Br-polymerylene-Br), wherein the at least one product is prepared from the B-based PCRA-polymeryl chain complex by contacting the latter with molecular bromine or equivalent in presence of a Group 1 or 2 metal alkoxide such as sodium methoxide.
  • a mono- or bis-bromo-terminated polymer i.e., polymeryl-Br or Br-polymerylene-Br
  • Fig. 4g shows an invention reaction for preparing at least one product comprising a mono-, di-, or tri-polymeryl-substituted methanol or bis-functionalized polymerylene analogs thereof, wherein R is (Ci-C 20 )hydrocarbyl), wherein the at least one product is prepared from the B-based PCRA-polymeryl chain complex by contacting the latter with carbon monoxide.
  • the third metal cation is aluminum cation
  • the third metal cation is aluminum cation
  • the contacting step is a displacement step that comprises the heat, i.e., is a thermal displacement reaction or displacement catalyst.
  • the thermal displacement reaction preferably is run without the displacement catalyst at elevated temperature and elevated pressure and with short residence time (i.e., time of contact) in the presence of excess of a sacrificial 1 -olefin to generate the carbon-carbon double bond-substituted poly olefin.
  • a preferred thermal displacement reaction is similar to the thermal displacement reaction described in U.S. Patent Number US 3,391,219 (e.g., see portion of Example 1 at column 7, lines 30-70).
  • the elevated temperature is at least 140 °C
  • elevated pressure is greater than ambient pressure (i.e., greater than 15 pounds per square inch (psi; 101 kiloPascals (kPa)).
  • the elevated temperature is 280 °C and the elevated pressure is 150 psi (1010 kPa).
  • the residence time is appropriate under the circumstances and readily determined.
  • the displacement catalyst preferably is colloidal Ni, Pt, or Co, nickel acetylacetonate, a cobalt carboxylate (e.g., cobalt 1-naphthenoate or cobalt acetate), nickel bis-l,5-cyclooctadiene (Ni(COD) 2 ).
  • the displacement catalyst optionally may be stabilized by combining it with a trivalent phosphorous ligand (e.g., triphenylphosphine).
  • a trivalent phosphorous ligand e.g., triphenylphosphine
  • the sacrificial olefin contains from 3 to 10 carbon atoms. Examples of sacrificial olefins are ethene, propene, and 1-butene.
  • Fig. 5a an invention reaction for preparing at least one product comprising a polymer (i.e., polymeryl-H), wherein the at least one product is prepared from the Al-based PCRA-polymeryl chain complex by contacting the latter with molecular oxygen (e.g., air).
  • molecular oxygen e.g., air
  • the contacting gives, after addition of water, a hydroxyl-substituted polyolefin (e.g., a hydroxy-telechelic polyolefin).
  • the at least one product is prepared from the Al-based PCRA-polymeryl chain complex by contacting the latter with the first olefin monomer (e.g., ethylene) in presence of displacement condition (e.g.
  • Fig. 5c shows an invention reaction for preparing at least one product comprising a mono- or bis-hydroxyl-terminated polymer (i.e., polymeryl-OH or HO-polymerylene-OH), wherein the at least one product is prepared from the Al-based PCRA-polymeryl chain complex by contacting the latter with an aluminum alkoxide (e.g., Al(OR) 3 , wherein R is (Ci-C 20 )hydrocarbyl) in water.
  • an aluminum alkoxide e.g., Al(OR) 3 , wherein R is (Ci-C 20 )hydrocarbyl
  • the invention process employs catalytic amounts of the NMOP catalyst(s). When more than one catalyst is employed in the invention process, each catalyst independently will be employed in a catalytic amount.
  • catalytic amount means less than a stoichiometric quantity based on number of moles of a product-limiting stoichiometric reactant employed in the invention process.
  • the catalytic amount is also equal to or greater than a minimum amount of the catalyst that is necessary for at least some product of the catalyzed reaction to be formed and detected (e.g., by mass spectrometry).
  • the minimum catalytic amount preferably is 0.0001 mole percent of the number of moles of a product-limiting stoichiometric reactant.
  • the product- limiting stoichiometric reactant for the invention catalyst typically will be an olefin monomer.
  • the catalytic amount of the non-metallocene-type precatalyst used to prepare the NMOP catalyst is from 0.001 mol % to 50 mol % of the moles of the first olefin monomer, more preferably at least 0.01 mol , still more preferably at least 0.05 mol %, and even more preferably at least 0.1 mol .
  • the catalytic amount is 40 mol % or less, and still more preferably 35 mol % or less.
  • Non-metallocene-type precatalysts useful for preparing, and non- metallocene-type catalysts prepared therefrom and useful as, the NMOP catalyst(s) are disclosed in US 2006/0199930 Al; US 2007/0167578 Al ; US 2008/0311812 Al ; US 7,355,089 B2; or WO 2009/012215 A2 and include the precatalysts of formulas (Al) to (A5), (Bl), and (B2):
  • Precatalyst (Al) is [N-(2,6-di(l-methylethyl)phenyl)amido)(2-isopropylphenyl)(a- naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teaching 04/24740, and having the structure:
  • Precatalyst (A2) is [N-(2,6-di(l-methylethyl)phenyl)amido)(2-methylphenyl)(l,2- phenylene-(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the
  • Precatalyst (A3) is bis[N,N" '-(2,4,6- tri(methylphenyl)amido)ethylenediamine]hafnium dibenzyl, and having the structure:
  • Precatalyst (A4) is bis((2-oxoyl-3-(dibenzo-lH-pyrrole-l -yl)-5-(methyl)phenyl)-2- phenoxymethyl)cyclohexane-l ,2-diyl zirconium (IV) dibenzyl, prepared substantially accordi aving the structure:
  • Precatalyst (A5) is [ ⁇ -2,6-diisopropyl-N-(2-methyl-3-(octylimino)butan-2- yl)benzeneamide]trimethylhafnium, prepared substantially according to the teachings of WO 2
  • Precatalyst (B l) is l,2-bis-(3,5-di-t-butylphenylene)(l-(N-(l- methylethyl)imino)methyl)(2-oxoyl) zirconium dibenzyl, and having the structure:
  • Precatalyst (B2) is l,2-bis-(3,5-di-t-butylphenylene)(l-(N-(2-methylcyclohexyl)- imino) :
  • each non-metallocene-type precatalyst preferably is rendered catalytically active, and thus prepares the corresponding NMOP catalyst, by contacting it to, or combining it with, the activating co-catalyst or by using an activating technique such as those that are known in the art for use with metal-based olefin polymerization reactions.
  • Suitable activating co-catalysts for use herein include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions).
  • alkyl aluminum means a monoalkyl aluminum dihydride or monoalkylaluminum dihalide, a dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkylaluminum.
  • USPN United States Patent Number
  • Examples of preferred polymeric or oligomeric alumoxanes are methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.
  • Preferred Lewis acid activating co-catalysts are Group 13 metal compounds containing from 1 to 3 hydrocarbyl substituents as described herein.
  • Group 13 metal compounds are tri(hydrocarbyl)-substituted-aluminum or tri(hydrocarbyl)-boron compounds, still more preferred are tri((Ci-Cio)alkyl)aluminum or tri((C 6 -Ci 8 )aryl)boron compounds and halogenated (including perhalogenated) derivatives thereof, even more especially tris(fluoro-substituted phenyl)boranes, still even more especially tris(pentafluorophenyl)borane.
  • the activating co- catalyst is a tris((Ci-C 2 o)hydrocarbyl) borate (e.g., trityl tetrafluoroborate) or a
  • ammonium means a nitrogen cation that is a ((Ci-C 2 o)hydrocarbyl) 4 N + , a
  • each (Ci-C 20 )hydrocarbyl may be the same or different.
  • Preferred combinations of neutral Lewis acid activating co-catalysts include mixtures comprising a combination of a tri((Ci-C 4 )alkyl)aluminum and a halogenated tri((C 6 -Ci 8 )aryl)boron compound, especially a tris(pentafluorophenyl)borane. Also preferred are combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane.
  • Preferred ratios of numbers of moles of (metal-ligand complex) : (tris(pentafluoro- phenylborane): (alumoxane) are from 1 : 1 : 1 to 1: 10:30, more preferably from 1 : 1 : 1.5 to 1:5: 10.
  • Bronsted acid salts for addition polymerization (pre)catalysts are disclosed in US 5,064,802; US 5,919,983; US 5,783,512.
  • suitable salts of a cationic oxidizing agent and a non- coordinating, compatible anion as activating co-catalysts for addition polymerization (pre)catalysts are disclosed in US 5,321,106.
  • suitable carbenium salts as activating co-catalysts for addition polymerization (pre)catalysts are disclosed in US 5,350,723.
  • Examples of suitable silylium salts as activating co-catalysts for addition polymerization (pre)catalysts are disclosed in US 5,625,087.
  • At least two of the foregoing activating co-catalysts are used in combination with each other.
  • An especially preferred combination is a mixture of a tri((Cr)
  • the ratio of total number of moles of each non-metallocene-type precatalyst to total number of moles of the at least one of the activating co-catalyst independently is from 1 : 10,000 to 100:1. Preferably, the ratio is at least 1 :5000, more preferably at least 1: 1000; and 10: 1 or less, more preferably 1 : 1 or less.
  • the number of moles of the alumoxane that are employed is at least 100 times the number of moles of the non-metallocene-type precatalyst.
  • the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of non-metallocene-type precatalyst is form 0.5: 1 to 10: 1, more preferably from 1 : 1 to 6: 1, still more preferably from 1 : 1 to 5:1.
  • the remaining activating co- catalysts are generally employed in approximately mole quantities equal to the total mole quantities of the non-metallocene-type precatalyst.
  • the invention process further employs a molecular weight control agent.
  • the molecular weight control agent is an ingredient (e).
  • examples of molecular weight control agents are trialkyl aluminum compounds and, preferably, hydrogen (H 2 ) gas.
  • BDAO Bis(diisobutylaluminum)oxide
  • Precatalyst (a non-metallocene-type precatalyst); diethylmagnesium (Et 2 Mg, DEM); diethylzinc (Et 2 Zn, DEZ); ethylene (C 2 H 2 ); IRGAFOSTM 168 (CAS No. 31570-04-4); IRGANOXTM 1010 (CAS No. 98584-37-3); ISOPAR E (CAS No. 64741-66-8; ExxonMobil Corporation, Houston, Texas, USA; hereinafter referred to as "Isoparaffin Fluid”); 1-octene; triethyl aluminum (Et 3 Al, TEA);
  • triethylborane Et 3 B, TEB
  • triethylgallium Et 3 Ga, TEG
  • triisobutylaluminum-modified methylalumoxane-3A MMAO-3A
  • tri(l-octyl)aluminum octyl 3 Al, TOA
  • Precatalyst (A) (a preferred non-metallocene-type precatalyst): is prepared according to the procedure of Example 7 of US 6,953,764 B2.
  • Method (A) FT-IR spectroscopy dissolve a polymer sample in 1 ,2,4-trichlorobenzene at 160 °C for 1 hr while shaking to give a solution having a concentration of 30 milligrams polymer per milliliter 1 ,2,4-trichlorobenzene (mg/mL). Deposit some of the 160 °C solution into individual cells on a silicon wafer, evaporate the 1 ,2,4-trichlorobenzene, and cool the polymer to room temperature. Analyze the resulting wafer using a Nicolet Nexus 670 FT-IR ESP infrared spectrometer to determine mole percent of octene within each sample.
  • Method (B) GPC determine weight average molecular weight (M w ), M n , and polydispersity index (PDI) values by analysis of a polymer sample on a SYMYXTM High-Throughput Gel Permeation Chromatographer. Utilize three Polymer Labs PLgel 10 ⁇ MIXED-B columns (300 millimeters (mm) x 10 mm) at a flow rate of 2.5 mL/minute in 1 ,2,4-trichlorobenzene at 160 °C. The molecular weight determination is deduced by using ten narrow molecular weight distribution polystyrene standards (from Polymer Laboratories, EasiCal PSI ranging from 580 g/mol to
  • the equivalent propylene -ethylene copolymer molecular weights are determined by using appropriate Mark-Houwink coefficients for polypropylene (as described by Th. G. Scholte, N. L. J. Meijerink, H. M. Schoffeleers, and A. M. G. Brands, Journal of Applied Polymer Science, 29, 3763-3782 (1984)) and polystyrene (as described by E. P. Otocka, R. J. Roe, N. Y. Hellman, P. M.
  • Method (C) DSC measure melting and crystallization temperatures of the polymer with a differential scanning calorimeter model DSC 2910, TA Instruments, Inc. Prepare polymer sample by pressing some polymer into a thin film, cut from about 3 milligrams (mg) to 10 mg portions of the film into a 6 mm diameter disks, accurately weigh them (about 50 mg total), placed in a light aluminum pan, which is then crimped shut.
  • Sequentially process the prepared polymer sample as follows: heat from room temperature to 210 °C at a heating rate of 10 °C/minute; hold at 210 °C for 4 minutes; cool to -40 °C at a cooling rate of 10 °C/minute; hold at -40 °C for 4 minutes; and heat to 215 °C at a heating rate of 10 °C/minute.
  • the instrument comprises a barrel and piston. Calibrate the instrument using Dowlex 2045.11G, which has a known MFR. Cut polymer samples into slices, and place the slices into the barrel of the Melt Flow Jr. Insert the piston into the barrel, and heat the placed samples to 190 °C for two minutes. Place a 2.16 kilogram (kg) weight on the top of the piston and allow the samples to heat for an additional five minutes while expelling polymer. Cut strands of expelled polymer at precise time intervals.
  • MOTIONTM flow meter Control and monitor the reactor, addition of ethylene thereto, and the heating/cooling thereof using a Camile TG process computer (Camile).
  • the dump valve operates to empty (void) contents of the reactor into a nitrogen gas-purged stainless steel (SS) dump pot that is vented to a nitrogen gas-purged 30 gallon (114 L) blowdown tank.
  • SS nitrogen gas-purged stainless steel
  • Example A Perform 24 runs using the batch procedure of Example A so as to prepare poly(ethylene 1- octene) copolymers.
  • PCSA or PCRA means believed to be acting as polymeryl chain shuttling agent, i.e., the second metal (Ci-C 2 o)hydrocarbyl but could be acting as polymeryl chain repository agent, i.e., the first metal (Ci-C 20 )hydrocarbyl;
  • PCRA or PCSA means the opposite of PCSA (or PCRA);
  • Cat. (A) means the Precatalyst (A); and min. means minutes.
  • Table 2 Catalyst efficiency and certain characterizations of poly(ethylene-co- 1-octene).
  • continuous flow reactor system 10 shown in Fig. 6.
  • continuous flow reactor system 10 comprises feed conduits 11 and 12, outlet conduit 13, and transfer conduits 14 and 15; reactor 30 (a 100 mL volumed EZE-Seal Reactor from the Autoclave Engineers division of Snap-tite, Inc., Erie, Pennsylvania, USA); oil bath jacket 40; agitator motor 50; FT-NIR cell 60; pressure control valve 70 (from Badger Meter Inc); three-way valve 72; air-actuated valve controller 73; prime receiver 80; and off -grade receiver 90.
  • Reactor 30 defines enclosed volumetric space 38 having a 100 mL volume.
  • Reactor 30 and agitator motor 50 are sealably in operative contact with stir shaft 35, which is in operative connection to a four-blade pitched impeller 36.
  • Separate containers ((not shown; sources of Feed Groups A and B and terminator and antioxidant/stabilizer packages) are in independent fluid communication with enclosed volumetric space 38 of reactor 30 via inlet conduits 11 and 12 as indicated by arrows 21 and 22, respectively.
  • Enclosed volumetric space 38 of reactor 30 is in sequential fluid communication with FT-NIR cell 60, pressure control valve 70, three-way valve 72 and air-actuated valve controller 73 via outlet conduit 13.
  • Three-way valve 72 is also in fluid communication with prime receiver 80 via conduit 14 and off -grade receiver 90 via transfer conduit 15.
  • Outlet conduit 13 is electrically heat traced, insulated, and defines a chemical package inlet (not shown) where indicated at point 71.
  • Reaction ingredients comprise Feed Groups A and B and terminator and the
  • Feed Group A comprises separate feeds of ethylene, 1-octene, and hydrogen gas. Ethylene and hydrogen gas are separately metered into conduit 11 using mass flow controllers (Brooks Instrument, Hatfield, Pennsylvania, USA). Ratio of ethylene to 1-octene in Feed A is from 1/1 (100%) to 116 th (17%) or ⁇ & (14%) of the ratios of ethylene/ 1-octene used in
  • Feed Group B comprises separate feeds of catalyst solution in toluene, PCRA solution, PCSA solution, and, optionally, an activator solution using Isoparaffin Fluid as solvent. Introduce feed streams into enclosed volumetric space 38 of reactor 30 via dip tubes as shown in Fig. 6. Liquid feeds (1-octene and the solutions) are separately fed from syringe pumps (Isco, Inc., a Teledyne Technologies Company, Lincoln, Kansas, USA). Preferred mole ratios of catalyst:PCSA:ethylene are 1:20:20,000.
  • a source (not shown) of a polymerization terminator package (small amount of water/propanol in toluene) and polymerization antioxidant/stabilizer package is in fluid
  • Examples 11a to 12f perform continuous-flow polymerization processes according to the procedure of Example B with Et 2 Zn as PCSA (i.e., second metal (Ci-C 2 o)hydrocarbyl) and Et 3 Al as PCRA (i.e., first metal (Ci-C 2 o)hydrocarbyl) at constant monomer conversion (about 91%) and various relative feed levels of Et 3 Al and Et 2 Zn. It is found that identical molar feed rates of Et 2 Zn and Et 3 Al each gave identical MFR values. For the expected narrow molecular weight distribution, samples with the same MFR should have the same M n and M w . Feed rates (a) to (d):
  • Zn cation A range of Et 2 Zn and Et 3 Al feed rates of 5% (Example 11a), 10% (Example 1 lb), 15% (Example 1 lc), 25% (Example 1 Id), and 50% (Example 1 le) mole fraction of Zn cation are tried in the reactor, all the while keeping the total of sum of Et 2 Zn and Et 3 Al feed rates constant at 6 ⁇ / ⁇ After quenching, MFR of resulting polyolefins are shown in Fig. 7 for at 0.05 zinc fraction, 0.1 zinc fraction, 0.15 zinc fraction, 0.25 zinc fraction, and 0.5 zinc fraction, respectively.
  • Examples 12a to 12f Invention > 0% mole fraction Zn cation to ⁇ 100% mole fraction Zn cation: A range of Et 2 Zn and Et 3 Al feed rates of 7% (Examples 12a and 12b), 14% (Example 12c), 22% (Example 12d), 34% (Example 12e), and 61% (Example 12f) mole fraction of Zn cation are tried in the reactor, all the while keeping the total of sum of Et 2 Zn and Et 3 Al feed rates constant at 6 ⁇ / ⁇ After quenching, MFR of resulting polyolefins are shown in Fig. 7 for at 0.07 zinc fraction, 0.14 zinc fraction, 0.22 zinc fraction, 0.34 zinc fraction, and 0.61 zinc fraction, respectively.
  • M n of the poly olefin of the invention Examples 1 la to 12f are unexpectedly decreased, which indicate a synergistic interaction occurs between the PCSA (e.g., Et 2 Zn) and PCRA (e.g., Et 3 Al) in the invention polymerization process.
  • PCSA e.g., Et 2 Zn
  • PCRA e.g., Et 3 Al
  • the invention composition and process are useful for and capable of (co)polymerizing olefin monomer(s) with a non-metallocene-type olefin polymerization catalyst (NMOP catalyst) in presence of the PCSA and PCRA to give a polyolefin-type
  • the PCSA reversibly shuttles the polyolefin-type (co)polymeryl chain between the NMOP catalyst and the PCRA.
  • the PCRA is effective for reversibly storing and functionalizing the polyolefin-type (co)polymeryl chain in situ as the metal-functionalized polyolefin in presence of the PCSA and NMOP catalyst.
  • the metal- functionalized polyolefin is useful for preparing a polyolefin-type polymer product that substantially lacks the metal (i.e., has less than 10 mole percent of initial amount of the metal) such as, for example, a polyolefin or telechelic polyolefin.
  • the invention process enables facile synthesis of the metal-functionalized polyolefin without substantially decreasing (i.e., decreasing by less than 10%) catalyst efficiency of the NMOP catalyst used therein.
  • the Examples also show that MFR of a polyolefin product is increased, and thus the M n of the polyolefin product is decreased compared to M n of a reference polyolefin product that has been prepared by a non- invention process employing the PCRA or PCSA, but not both.

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Abstract

L'invention concerne d'une façon générale un procédé de préparation d'une polyoléfine fonctionnalisée par du métal et une composition utile dans celui-ci, et la polyoléfine fonctionnalisée par du métal préparée de cette manière, ainsi que de nouveaux polymères non métalliques préparés avec celle-ci.
PCT/US2011/059326 2010-11-04 2011-11-04 Navette double de chaînes polymeryl de polyoléfine WO2012061706A1 (fr)

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WO2014099440A1 (fr) * 2012-12-20 2014-06-26 Exxonmobil Chemical Patents Inc. Polyméryles métalliques et surfaces solubilisées en polymère dérivées de ceux-ci

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